Disazo dyestuffs containing a heterocyclic bridging member

ABSTRACT

Disazo dyestuffs of the formula in which D1 and D2 each represents the residue of a diazo component of the benzene or naphthalene series containing at least one and not more than three sulpho groups; X, Y and Y1 each represents hydrogen, trifluoromethyl, lower alkanesulphonyl, lower alkyl, lower alkoxy, phenoxy, chlorine, bromine or lower carboxylic acylamino; R1, R2 and R3 each represents hydrogen, lower alkyl or lower alkyl substituted by cyano, hydroxyl, lower acyloxy or esterified carboxyl; n 1, 2 or 3 and Z&#39;&#39; represents the bridge member of the formula

United States Patent [191 de Montmollin et a1.

[ July 15, 1975 DISAZO DYESTUFFS CONTAINING A HETEROCYCLIC BRIDGINGMEMBER [63] Continuation of Ser. No. 109,664, Jan. 25, 1971, abandoned,which is a continuation-in-part of Ser. No. 753,901, Aug. 20, 1968, Pat.No. 3,642,764.

[30] Foreign Application Priority Data Aug. 25, 1967 Switzerland11938/67 July 17, 1968 Switzerland 10745/68 [52] U.S. Cl. 260/153;260/152; 260/154;

260/155; 260/156; 260/157; 260/158; 260/249.8; 260/295 R; 260/295.5 R;260/326.46; 260/332.2 C;

[51] Int. Cl C0911 33/16 [58] Field of Search 260/152, 153, 156, 157,260/154 [56] References Cited UNITED STATES PATENTS 3,271,383 9/1966Yamaya et al 260/156 3,415,809 12/1968 Fisher et a1. 260/158 3,642,7642/1972 de Montmollin et al 260/152 3,691,148 9/1972 Peter et a1. 260/1523,712,881 l/l973 Angliker et a], 260/157 3,749,576 7/1973 Piller 260/1563,770,718 11/1973 Angliker et al. 260/156 3,804,630 4/1974 Loefed et al260/153 Primary Examiner-Henry R. Jiles Assistant Examiner-Robert W.Ramsuer Attorney, Agent, or Firm-Joseph G. Kolodny; Edward McC. Roberts;Michael W. Glynn [57] ABSTRACT Disazo dyestuffs of the formula in whichD and D each represents the residue of a diazo component of the benzeneor naphthalene series containing at least one and not more than threesulpho groups; X, Y and Y each represents hydrogen, trifluoromethyl,lower alkanesulphonyl, lower alkyl, lower alkoxy, phenoxy, chlorine,bromine or lower carboxylic acylamino; R R and R each representshydrogen, lower alkyl or lower alkyl substituted by cyano, hydroxyl,lower acyloxy or esterified carboxyl; n 1, 2 0r 3 and Z represents thebridge member of the formula where B represents CO-, SO or loweralkylene; X and Y each represents -O, NR (wherein R is hydrogen or loweralkyl), or a direct linkage: R represents a diazine, triazine, furan,pyridine, pyrrole or thiophene residue; p, q and r 1 or 2, the sum ofp+q+r must be at least 4. The dyestuffs are suitable for dyeing andprinting materials of minimal origin, polyamide fibres, polyurethanesand other such materials. The obtained dyeings and prints exhibitexcellent light and wet fastness.

7 Claims, No Drawings DISAZO DYESTUFFS CONTAINING A HETEROCYCLICBRIDGING MEMBER gen atom or preferably a low-molecular (containing 1 to4 carbon atoms) substituted or unsubstituted alkyl group, which may belinked with the residue A or A in the ortho-position to the group NR Ror NR R to form a ring; R represents a low-molecular substi tuted orunsubstituted alkylene group; A, and A each represents a benzene ornaphthalene residue in which the azo group and the group NR R or NR Rare attached in the 1,4-position to each other; D and D each representsthe residue of an aromatic or heterocyclic diazo component containing asulpho group and if desired a fibrereactive group, and Z represents adivalent bridge having no dyestuff characteristics.

Specially valuable are dyestuffs of the present invention of formulae(where D represents the residue of a diazo component containing at leastone strongly acidic group imparting solubility in water and if desiredazo groups, A represents the residue of a coupling component of thebenzene or naphthalene series containing the amino group in theparaposition to the azo group, R and R each represents a hydrogen atomor an alkyl or arallkyl residue which may be substituted) are linkedthrough their coupling components by a divalent bridge Z (having nodyestuff characteristics), which is bound either through the residues Rand/or R or directly to the residues of the coupling components.

More particularly the present invention provides new disazo or polyazodyestuffs, in which two of the same or different azo dyestuff residuesof the general formula are linked through a divalent bridge member Z, inwhich formulae R R and R each represents a hydrowhere D and D eachrepresents the residue of a diazo component of the benzene ornaphthalene series containing at least one and not more than threesulpho groups and if desired a fibre-reactive group; X, Y and Y eachrepresents hydrogen, trifluoromethyl, alkanesulphonyl, alkyl, alkoxy,aryloxy, halogen or acylamino; R R and R each represents hydrogen, alkylor substituted alkyl; n 1, 2 or 3 and Z represents a bridge member ofthe formula where B represents a CO, S0 or lower alkylene bridge; X andY each represents an oxygen atom or a nitrogen (especially an NH) bridgeor a direct linkage, and the two Xs or Ys and B may be different fromeach other; R represents a substituted or unsubstituted heterocyclicresidue; p, q and r may each be equal to l or 2, but the sum p+q+r mustbe at least 4. It is obvious that the residues D D R R R X, Y and Ypresent on both sides of the bridge member Z may be different from eachother.

The new dyestuffs may be obtained for example by either (a) reacting twodyestuffs of the formula R (Ia) DN=N-- A N with each other or with abifunctional compound containing two reactive atoms or groups terminallybound (VI a) to a bridge Z, which may react with the reactive atoms orgroups of the azo dyestuffs. In formula (Ia) D,A,R and R have theabovementioned meanings but in the residue A or R and/or R one hydrogenatom is 'replaced by a reactive atom or a reactive group. For instance,two azo dyestuffs of the formula where Q represents a reactive atom or areactive group, for example a carboxyl or sulphonic acid group or theiracid halides, or an acylatable group, especially an amino, mercapto orhydroxyl group or their reactive derivatives, and where R R R R A D andD have the above meanings, but where R, may also represent a directlinkage, may be reacted together or with a bifunctional compound of theformula where Z has the above mentioned meaning and both the Q srepresent reactive atoms or reactive groups as defined for O which mayreact with Q; or

b. a compound, consisting of two coupling components of the formulawhich are linked through a bridge member Z, may be coupled on both sideswith diazo compounds of amines of the formula D-Nl-h; for example, acompound, containing two residues of coupling components of the formulaelinked together through a bridge member Z, where A A R R R R and Z havethe above meanings, may be coupled with diazo compounds of amines of theformulae D,--NH and D NH or 0. substituents may be subsequentlyintroduced into the disazo or polyazo dyestuffs produced by coupling orcondensation, for instance a reactive group by acylation.

Azo dyestuffs having the same components A, A A D, D D R R R and R maybe used for the various processes so that symmetrical disazo or polyazodyestuffs are obtained; likewise, starting materials may be used inwhich one or more of these components are different so that asymmetricaldisazo or polyazo dyestuffs are obtained. The two residues Q or Q may ofcourse also be different from each other.

Suitable azo dyestuffs for the process (a) are those which may beobtained by coupling diazo compounds of amines containing sulpho groups,preferably those of the aromatic or'het'erocyclic series, with anydesired coupling components which must contain a reactive atom bound tothe nucleus or to an N-alkyl residue, or a reactive group of the typementioned above.

The following amines containing sulpho groups but no fibre-reactiveresidue may be mentioned:

amines of the benzene series, for example 0-, morp-aminobenzene-sulphonic acid, l-aminobenzene-2,4- or2,5-disulphonicacid, 4-aminodiphenyl sulphonic acid; 1 I

amines of the naphthalene series, for example l-aminonaphthalene-4-,-5-, -6-, -7- or -8-sulphonic acid, 2-aminonaphthalene-6-sulphonic acid,l-aminonaphthalene-2,4-, -3,6-, -3,8- or -4,8- disulphonic acid,2-aminonaphthalene-4,8-, -5,7- or -6,8-disulphonic acid,l-amino-4-benzoylaminonaphthalene-3,6-, or -4,6-disulphonic acid, 2-aminonaphthalenel ,5 ,7-trisulphonic acid, l-aminonaphthalene-2,4,8-,-3,6,8- or -4,6,8- trisulphonic acid;

amines of the pyrene series, for example 3-aminopyrene-5-sulphonic acid,3-aminopyrene-5,8- or 5,l-disulphonic acid, 3-aminopyrene-5,8,l0-trisulphonic acid;

amines of the heterocyclic series, for example 2-aminobenzthiazole-6-sulphonic acid, dehydrothiotoluidinedisulphonicacid;

amines with azo groups, for example 4- aminoazobenzene monoordisulphonic acid;

The following may be mentioned as amines containing sulpho groups and afibre-reactive residue:

amines of the "benzene series, for example 4- or 5-acylamino-2-aminobenzene-l-sulphonic acid;

amines of the naphthalene series, for example 2-acylamino-6-aminonaphthalenel ,S-disulphonic acid;

amines of the stilbene series, for example 4-acylamino-4'-aminostilbene-2,2-disulphonic acid;

amines with azo groups, for example 4-acylamino-4-aminoazobenzen'e-2-sulphonic acid.

Amines without sulphonic acid groups bound to the nucleus may also beused, provided that the fibre reactive acylamino residue contains asulphonic acid group. The following may bementioned as examples:

amines of the benzene series, for example 2-, 3-, or 4-acylaminoaniline,-'2- or 4-acylamino-4- aminodiphenyl, 2- or4'-acylamino-2'-aminodiphenyl and the corresponding methanes; I r

amines of the naphthalene series, for example 1-acylamino-5-aminonaphthalene.

The amines mentioned here are by no means the only compounds suitable asthe diazo components. Inter alia, amines having carboxyl groups as thegroups imparting solubility in water, for example anthranilic acid andamines containing other substituents, for example hydroxyl groups, forexample aminophenols, aminonaphtholsulphonic acid and others may also beused. Metal complexes, for example Cu, Ni or C0 complexes may be used,provided complex forming substituents are present in the o-position tothe azo groups.

The fibre-reactive acylamino residue may be introduced according to theusual-methods by selective acylation of one of the amino groups of thediazo component or of the finished azo dyestuff. The following may bementioned as acylati'n'g' agents containing a fibrereactive residue: Y 1

diphenyl oxides, sulphones or [Ill fl-chloroacetyl chloride or bromide,,d chloroor ,G-bromo-propionyl chloride or bromide, or,fil-dichloroordibromo-propionyl chloride or bromide, acryl chloride,ot-chloroor oz-bromoacryl chloride or bromide, trichloroacryl chloride,chloroacrotonyl chloride, propiolic acid chloride;3-nitro-4chlorobenzenesulphonic acid or carboxylicacid chloride, 2,2,33-tetrafluorocyclobutane-l-carboxylic acid chloride and especiallyheterocyclic acid halides and their derivatives, for example theIZ-chlorobenzoxazole carboxylic acid chlorides, Z-chlorobenzthiazolecarboxylic or sul phonic acid chlorides, and especially the followingcompounds containing at least 2 nitrogen atoms as the hetero atoms of a6-rnembered heterocycle:

4-,5-dichloro-l-phenylpyridazone carboxylic or sulphonic acid chloride,4,5-dichloropyridazone propionic acid chloride, l,4dichlorophthalazinecarboxylic or sulphonic acid chloride, 2,3-dichloroquinoxalinecarboxylic or sulphonic acid chloride, 2,4- dichloroquinoxalinecarboxylic or sulphonic acid chloride, 2-methanesulphonyl-4chloro-6-methylpyrirnidine, tetrachloropyridazine,2,4-bismethanesulphonyl-6-methylpyrimidine, 71,4,6-trior2,4,5,6tetrachloropyriinidine, 2,4,6-tri-- or 2,4,55,6-tetrabromopyrimidine, 2-rnethanesulphonyl-4,5-dichloro-o-rnethylpyrimidine, 2, l-dichloropyrimidine- -sulphonic acid,5-nitroor 5 cyano-2,4,6- trichloropyrimidine,2,6-bismethanesulphonylpyridinel-carboxylic acid chloride,5-nitro-6-methyl-2,4-dichloropyrimidine, 2,6-dichloropyrirnidine-4-carboxylic acid chloride, .2,6-dichloropyrimidine-5-carboxylic acid chloride, 2,4-dichloropyrimidine-4-sulphonic acid chloride, 2,4-dichloropyrlmidine-Ssulphonic acid chloride, 2,4,6trichloro-l,3,5-triazine, as Well as 2,4,64ri-(benzenesulphonyD-l,3,5-triazine and 4,6-dichloro- 1,3,5-triazinessubstituted in the 2-position by an aryl or alkyl residue, for example aphenyl, methyl or ethyl residue, or by a residue of an aliphatic oraromatic mercapto compound bound through the sulphur atom or hydroxylcompound bound through the oxygen atom, or especially by an Nl-l -groupor by the residue of an aliphatic, heterocyclic or aromatic aminocompound bound through the nitrogen atom. Compounds in which theresidues may be bound to the triazine nucleus in "the 2-position by areaction with trihalogen triazines are, for instance, the following:

aliphatic or aromatic mercapto or hydroxyl compounds, for examplethioalcohols, 'thioglycollic acid, thiourea, thiophenols, methanol,ethanol and isopropanol, glycollic acid, phenol, chloroor nitrophenols,phenol carboxylic and sulphonic acids, naphthols, naphtholsulphoni-cacid and so on, but especially monia and. compounds containingacylatable amino groups, for example hydroxylarnine, hydrazine,phenylhydrazine, phenylhydrazine sulphonic acids, carbamic acid and itsderivatives, sen1iand thiosemicarbazides and carbazrones; methyh,ethylisopropyl--, methoxyethyh, methnxypropylarnine; dirncthyl diethyl,rnethylphenyl. ethylenephenylarnine, chloroethylarnine, ethanolarnines,propanol'amines, benzylarnine, cyclohexylamine. morpholine, piperidine,piperazine, aminocarbonic acid esters, glycine ethyl ester,aminoethanesulphonic acid, N-methylaminoethancsulphonic acid, especiallyaromatic amines, for. example aniline, l lanethylaniline, toluidines,xylidines, chloranilines, por m-arninoacetanilide, nitroanilines,arninophenols,

amines, aminonaphthols, diaminonaphthalenes and es pecially anilinescontaining acidic groups, for example sulphobenzylamine, sulphanilic,metanilic or ortlianilic acid, aniline disulphonic acids, aminobenzylsulphonic acids, aniline-cu-methariesulphonic acid, aminodibenzoicacids, naphthylarnino mono-, diand trisulphonic acids, aminobenzoicacids, for example 2-hydroxy'5- aminobenzoic acid, aminonaphtholmono',-diand trisulphonic acid and so on, coloured compounds or compoundshaving dyestuff characteristics, for example 4-nitro-4'aminostilbenedisulphonic acid, 2-nitro-4'- aminodiphenylamino-4,3'-stilbenedisulphonic acid, 2-nitro-4'aininodiphenylaminc-4,3'-disulphonic acidand especially arninoazo dyestuffs or aminoanthraquinones orphthalocyanines that contain at least one reactive amino group.

"I he introduction or" the substituent into the 2- position of thetriazine residue may be carried out after the condensation with thestarting diarnine or after the production or" the dycstuff.

Other examples of fibre-reactive residues, apart from those introducedby acylation, are the following: the vinylsulpho, the ,B-sulphatoorthiosulphatoethylsulphone, the ,B-thiosulphatopropionylamido-, theB-thiosulphatoethylsulphonyamidoor the sulphonic acid-N,,B-sulphatoethylamido groups, which may be introduced in some other way,preferably into the diazo component, for example by ester or thioesterformation.

The amines or aminosulphonic acids used in the process of the. presentinvention or acyl derivatives thereof may be diazotized and coupled inthe usual manner.

The coupling may take place in the presence of agents that stronglyfavour coupling in the 4-position to the amino group or hinder couplingin a position adjacent to the amino group.

The coupling components of the benzene or naphthalene series to becoupled with the diazo compounds of the above mentioned amines mustcontain a reactive atom or a reactive group and must be capable ofcoupling in the para-position to an amino group. This atom or group maybe linked either directly or through an alkylene bridge to the benzeneor naphthalene nucleus; or the reactive atom or reactive group may bebound to the coupling component through an N-alkylene bridge of theamino group.

Coupling components may have the following formulac, for example inwhich A A R R Q, n, X, Y and Y have the meanings given for formulae(lla), (llla), (IV), (V) and (VI). X and Y preferably each represents ahydrogen atom, a methyl, ethyl, methoxy, ethoxy, phenthio or phenoxygroup and Y represents one of the above mentioned substituents or achlorine or bromine atom, a trifluoromethyl or an acylamino group, inwhich the acyl residue may be the residue of an organic monocarboxylicacid, an organic monosulphonic acid, for example methane-, ethaneorp-toluene monosulphonic acid, or the residue of a carbamic acid or of acarbonic acid monoester or monoamide, for example phenoxycarbonyl,methoxycarbonyl or aminocarbonyl.

The groups R,, R and R may each represent a hydrogen atom, an alkyl orsubstituted alkyl group, for example a halogenated alkyl group, forexample B-chloroethyl, B, B, B-trifluoroethyl, B, y-dichloropropyl,B-cyanoethyl; alkoxyalkyl, for example B-ethoxyethyl or S-methoxybutyl;hydroxyalkyl, for example B-hydroxyethyl, B, y-dihydroxypropyl;nitroalkyl, for example B-nitroethyl; carbalkoxy, for exampleB-carbo(methoxy, ethoxy or propoxy )ethyl, B- or 'y-carbo(methoxy orethoxy)propyl; acylaminoalkyl, for example B-( acetyl orformyl)aminoethyl; acyloxyalkyl, for example B-acetyloxyethyl, B,y-diacetoxypropyl; B-(alkyl or aryl)-sulphonylalkyl, for exampleB-methanesul- 8 phonylethyl, B-ethanesulphonylethyl orB-(pchlorobenzenesulphonyl)ethyl; alkylor arylcarbamoyloxyalkyl, forexample B-methylcarbamyloxyethyl and B-phenylcarbamyloxyethyl;alkoxycarbonyloxyalkyl, for example B-(methoxy, ethoxy orisopropoxy)carbonyloxyethyl, y-acetamidopropyl, B-(p-nitrophen0xy)ethyl,B-(p-hydroxyphenoxy)ethyl, B, B(B-acetylethoxycarbonyl)-ethyl,B-[B'-(cyano, hydroxy, methoxy or acetoxy)ethoxycarbonyH-ethyl,cyanoalkoxyalkyl, B-carboxyethyl, B-acetylethyl, 'y-aminopropyl,B-diethylaminoethyl, B-cyanoacetoxyethyl and B-benzoyloxyethyl groups.These groups generally contain no more than eight carbon atoms andpreferably no more than six.

Tetrahydroquinoline or benzomorpholine or their derivatives for example,are used as the coupling component when the group R R or R is bound to aring with the aromatic nucleus.

The following may be mentioned as examples of such coupling componentsin which Q in the formulae given represents a reactive atom or areactive group of the given type, for example, a halogen atom, asulphato group or an aryl or alkylsulphonyloxy group:

-Continued The azo dyestuffs obtained from the abovementioned diazo andcoupling components by coupling and if desired subsequent acylation andwhich contain in the residue of the coupling component a reactive atomor a reactive group, may be linked by condensation with bifunctionalcompounds or directly with each other according to production method a),simultaneously or in any desirable sequence. Ester or amide bridges maybe formed during this process, for instance by the reaction of acids,especially carboxylic acids or their derivatives, for exampleanhydrides, esters, halides or of isocyanates with hydroxy or aminocompounds. Oxygen or nitrogen bridges may be formed, for instance by thereaction of hydroxy or amino compounds with compounds containing readilysplittable multi-valent bonds or readily removable groups (for instancesulphato groups) or atoms (for example halogen atoms), or of compoundswith readily openable heterocyclic rings (for example epoxy compounds)with compounds containing readily removable hydrogen atoms. Thesereactive atoms or groups correspond to the abovementioned residuesdefined as Q or Q; they may be present in the coupling components or thecompounds used for linking. For example, the hydroxyl, amino or epoxidegroups may occur in the compound QZ-Q' (as Q) and the acids or acidderivative groups or hydrogen atoms in the coupling components of theazo dyestuffs reacting with those groups may occur in these dyestuffs,(as Q or vice versa); or the compound Q'Z-Q' may, for example, contain ahydroxyl, amino or epoxide group on one side and a reactive hydrogenatom or an acid or an acid derivative group on the other. The reactionof the azo dyestuffs with the compounds used as the bridge member iscarried out by the usual methods.

The bridge members formed during the reaction have preferably thegeneral composition given in formula VI and correspond, for example, tothe following formulae:

-OSO,Y"-RY"OSO where X" and Y" each represents -O, S-, NR"- or Nl-l-;and R" represents a substituted or unsubstituted heterocyclic bridge.

The following acids (or their halides, anhydrides, or esters) areexamples of suitable bifunctional reactants: 2,5-thiophenedicarboxylicacid, furandicarboxylic acid, pyridinedicarboxylic acid, and also theheterocyclic diisocyanates (which may be prepared in situ), for example,diisocyanates of benzofuran or those containing urea or uretdionegroups, for example, l,3-bis-(4'- methyl-3 -isocyanatophenyl)-uretdione.

\ outcome The production of carbonic acid diesters or diamide urea)bridges or of carbamic acid ester bridges may be carried out directlywith phosgene or in steps, that is by first producing the chloroformicacid ester of one azo dyestuff. Bis-carbonic acid diester or diamidebis-urea) bridges or bis-carbamic acid ester bridges or combinations ofsuch bridges may be obtained by reacting 2 mols of the chloroformic acidester of an azo dyestuff with one mol of a diol, a diamine or a dithiolto obtain diurethane, bis-(thiourethane) or a bis-urea compound.

The dyestuffs of the present invention may also be obtained according tothe production method (b) by coupling two coupling components (bound toeach other through a bridge linkage) with diazotized amines. Examples ofsuitable coupling components are the following of the formulae (IVb) TXQat 2 3 14 in which X, Y, Y Z, R,, R R and n have the same meanings asgiven for formulae (IV) and (V).

Such bifunctional coupling components may be manufactured in principlein the same manner as described for method (a) for the linking of azodyestuffs. Method (b) is specially suitable for the production ofdyestuffs containing a bridge linkage bound to the nucleus of thecoupling component, since a large number of readily available startingmaterials exist, which may be easily linked due to the presence ofreactive, nucleus-bound atoms, for example, hydrogen atoms or groups,for example, the isocyanate, carboxyl or hydroxyl groups, or ofnucleus-bound groups capable of conversion into reactive groups (forexample by the reduction of nitro groups to amino groups or bychlorination of carboxyl groups to carboxychloride groups), and in whichthe amino group para to the coupling position need not be present at thestart but may be produced subsequently, for instance by reducing a nitrogroup (which may be followed by a conversion into a secondary ortertiary amino group).

When at least one of the two azo residues is directly bound to thebridge linkage the diamines used as bifunctional coupling components arenew compounds, i.e. they correspond for example to formula (lVb) andform part of the invention. They are manufactured as mentioned above bylinking, often advantageously using as starting materials aromatic nitrocompounds and reducing the bis-nitro compounds obtained after thelinkage by known methods (for instance catalytically or in the presenceof acids) and if desired followed by alkylation, for instance, byreaction with alkyl halides, for example, ethyl chloride, monoepoxides,for example, ethylene oxide, halogenhydrine, for example, ethylenechlorohydrin or ethyleneimine, and, if desired, carrying out furtherreactions with the alkyl groups present at the nitrogen atom, forinstance, acylating B-hydroxy or B-aminoethyl groups with acidchlorides, anhydrides or isocyanates.

Other methods of production are available apart from the twoabove-mentioned most usual methods by condensation or addition of thetwo azo dyestuffs to the compound used as the bridge linkage, or bycoupling the two diazo components to a compound linked to both couplingcomponents through a bridge linkage. For instance, in method (c) a fibrereactive residue may be introduced into disazo or polyazo dyestuffs thatalready contain two azo dyestuff residues bound through a bridge member,and of which at least one contains an acylatable group (especially anamino group) in the diazo component, by subsequent condensation withacylating agents containing a fibre-reactive residue. Suitable acylatingagents are those mentioned above. Subsequently, if desired, (forinstance after acylation with a trihalogen triazine) a halogen atom inthe triazine ring may be replaced, for example, by an amino group.

SOH

SO H

The dyestuffs obtained by the present process and its variants are newsubstances. They are suitable for dyeing and printing the most variedmaterials, for example of animal origin, for example, leather, silk,wool and especially polyamide fibres as well as polyurethanes ormixtures containing such fibres; the fibre-reactive dyestuffs are alsosuitable for dyeing cellulosic fibres, for

example, cotton. Wool and polyamide fibres may be dyed in a neutral orespecially a weakly acidic bath, for example, an acetic acid bath. It isrecommended in certain cases to add polyglycol ether derivatives to thedyebath so as to obtain uniform dyeing, especially when using dyestuffswith reactive groups, and is especially recommended for W001. Thesepolyglycol ether derivatives should contain on the average at least tenCl-l CH -O groups and be derived from monoamines containing an aliphatichydrocarbon residue of at least 20 carbon atoms. The new dyestuffs takevery well to polyamide fibres, and the resultant colorations and printsexhibit excellent light and wet fastness, especially good fastness towashing, fulling and water and frequently require no further treatment.Wool dyed with fibre-reactive dyestuffs also exhibits good fastness toperspiration. 4

Dyestuffs containing reactive groups are also suitable for dyeing andprinting cellulosic materials. In this case, however, the dyestuffs ofthe present invention require fixation by heat treatment in the presenceof alkali, for example, sodium carbonate, sodium hydroxide or trisodiumphosphate.

Unless otherwise indicated, parts and percentages in the followingExamples are by weight and temperatures are given in degrees Centigrade.

EXAMPLE 1 5.06 Parts of aniline-2,5-disulphonic acid are dissolved in125.parts of water and to the solution 5 parts of concentratedhydrochloric acid and 5 parts of a 4N NaNO solution are added. Theresultant diazo solution is added dropwise at a temperature between 5 to10 to a solution of 6.96 parts of the amide of thiophene-2,5-dicarboxylic acid and N-bis-B-acetoxyethyl-foaminoaniline in 100parts of acetone, 20 parts of conc'entrated hydrochloric acid and partsof water. The resultant mixture is stirred overnight at a temperaturebetween 0 to 5C, adjusted to a pH-value between 6.5 to 7 with a 30%solution of sodium hydroxide and evaporated in a rotary evaporator. Asalt-containing dyestuff corresponding tothe formula is obtained, whichdyes nylon yellow tints fast to wetting and light.

The amines shown in column I of the following Table may be diazotized ina like manner and coupled at a molar ratio of 2:1 withthe couplingcomponenets shown in column II to obtain disor tetrakisazo dyestuffswhich dye nylon the shades shown in column I.

-Continued yellow l\' (3 H '-QCOCH 2 4 J 2 "a n N SOBH v A (C H4ObUuII351 1 H035 ll I l claret K z 2 orange SO H orange 54) orange CI-I CONH.

.-3C SO2 55) I I scarlet do I y u CE 'Br-CHBr-CO CH -CHBr 3 56) l lorange 31 v CONH NH 57) yellow 58) H claret -Continued I ll lll a c \T oii CH 3 CH O-h C \1 5 l. L 66 r n Nk o a ge XHA PNH 3 01 M CH 5 i 67),QN\ 1?: N N yellow NH -CG0n-C& Br H macocs 3 N 2 4 Br r i 3 00H Cl C 7N N 52y 68) N\ I H u orange .-C ;I 1\r. l\.-: 0 n

7 NHCOCH A 3 EXAMPLE 2 is precipitated after completion of thecondensation by 442 Parts of the am dyestuff of the formula 0 additionof sodium chloride, filtered and dried in vacu- "o o. It corresponds todyestuff No. 59 of the Table of EX- 5 ample l and dyes polyamide fibresyellow tints fast to v wetting and light.

2 4- z According to the same method, the other dyestuffs SO. H indicatedin the Table of Example 1 can be obtained if 5 the monoazo dyestuff or(m the case of assymmetric Cil end products) both monoazo dyestuffs arefirstly manufactured, and there are subsequently condensed with thecorresponding dihalogen or trihalogen triazines,

tetrahalogen pyrimidines, pyrrole-, thiopheneor pyridinecarboxylicacids.

We claim: 1. A disazo dyestuff of the formula tetrafluorocyclobutanel-carboxylamino, 2- chlorobenzoxazole carboxylamino, 2-chlorobenzthiazole carboxylamino, 2- chlorobenzthiazole sulphonylamino,2,5-dichloro-1- phenylpyridazone carboxylamino, 2,5-dichlorolphenylpyridazone sulphonamino, 4,5- dichloropyridazone propionylamino, 1,4- dichlorophthalazine carboxylamino, 1 ,4- dichlorophthalazinesulphonamino, 2,3- dichloroquinoxaline carboxylamino, 2,3-dichloroquinoxaline sulphonamino, 2,4- dichloroquinoxalinecarboxylamino, 2,4- dichloroquinoxaline sulphonamino, 2-

methanesulphonyl-4-chloro-6-methylpyrimidino, tetrachloropyridazino2,4-bis-methanesulphonyl-6- methylpyrimidino, 2,4,6-trior 2,4,5 ,6-tetrachloropyrimidino, 2,4,6-trior 2,4,5 ,6- tetrabromopyrimidino,2-methanesulphonyl-4,5- dichloro-6-methylpyrimidino, 2 ,4-dichloro-5-sulfopyrimidino, S-nitroor 5-cyano-2,4,6- trichloropyrimidino 2,6-bismethanesulphonylpyridine-4-carboxylamino, 5 -nitro-6-methyl-2,4-dichloropyrimidino, 2,6-dichloropyrimidine-4-carboxylamino, 2,6- dichlo ropyrimidine-S-carboxylamino, 2,4-

toluidino xylidino, chlorophenylamino, nitrophenylamino,o-acetamidoanilido, pacetamidoanilido aminoanilino, aminotoluidino,

anisidino, phenetidino, diphenylamino, naphthylamino,hydroxynaphthylamino, aminonaphthylamino, sulfobenzylamino,hydroxyphenylamino, sulfophenylamino, disulfophenylamino,B-sulfotoluidino, N-sulfomethyl anilino, bis(carboxyphenyl) amino, mono,-di-, or tri-sulfo-naphthylamino, 3-carboxy-4- hydroxyanilino, mono-,di-, or tri-sulfonaphtholamino, disulfo-4'-nitrostilbene-(4)-amino, 3',4-disulfo-2- nitro-stilbene-4'-aminodiphenylamino, or 2-nitro, 4,3-disulfo-4-aminodiphenylamino, nitroanilino, nitrotoluidino, or 0- ormcarboxyphenylamino;

X, Y and Y each is hydrogen, trifluoromethyl, lower alkanesulphonyl,lower alkyl, lower alkoxy, phenoxy, chlorine, bromine or loweralkanoylamino;

R R and R each is hydrogen, lower alkyl or lower alkyl substituted bycyano, hydroxyl, acetyloxy, carbomethoxy, carboethoxy, or carbopropoxy;

n 1, 2 or 3 and Z represents the bridge member of the formula wherein Brepresents -CO, SO or lower alkylene; X and Y each represents -O, --NRwhere R is hydrogen or lower alkyl or a direct linkage; R representsthiophene, furan, benzofuran, pyridine, pyrrole, pyrimidine substitutedby chlorine, triazine substituted by chlorine, fluorine, methyl, ethyl,phenyl, N,N- bis-(B-hydroxy-ethyl)-amino or B-ethoxyethoxy or3,3bis(mtolylene) uretdione; p and r 1 or 2, q=2 and the sum of p+q+rmust be at least 4.

2. A disazo dyestuff as claimed in claim 1, wherein X' and Y' representNl-l-, the two B, X, Y, p, q and r are the same, and in which at leastone of the residues R R and R represents ethyl or ethyl substituted inl3-position by cyano, hydroxyl, acetyloxy carbomethoxy, carboethoxy orcarbopropoxy.

3. A disazo dyestuff as claimed in claim 9 of the formula 3 ,895 ,004 3334 in which X represents hydrogen, methyl or methoxy; in which Y" and Yeach represents hydrogen, chlo- R and R each represents hydrogen orlower alkyl and rine, lower alkyl, lower alkoxy, benzoylamino or lowerZ" has the formula alkanoylamino.

6. A disazo dyestuff as claimed in claim 1, wherein D represents theformula 4. A disazo dyestuff as claimed in claim 3, wherein X,represents hydrogen and R and R each represent lower alkyl containingnot more than 4 carbon atoms X or acetyloxy substituted lower alkyl.

5. A disazo dyestuff as claimed in claim 1 of the for- 110 50011 CH (NH)SO X mula V Y" 1 5 $2 F2 D -MNQ --iCH Z"(CH -N I I where n l or 2, one Xis bound to the azo group and the other is -H, Cl, -CH or OCH:;,

7. A disazo dyestuff as claimed in claim 1, wherein N:N D thesubstituent on D; and D is chloroacetylamino, a,,B-dibromopropionylamino, acrylamino, a-bromoacrylamino orB-sulphatopropionylamino.

1. A DISAZO DYESTUFF OF THE FORMULA
 2. A disazo dyestuff as claimed inclaim 1, wherein X'' and Y'' represent -NH-, the two B, X'', Y'', p, qand r are the same, and in which at least one of the residues R2, R1 andR3 represents ethyl or ethyl substituted in Beta -position by cyano,hydroxyl, acetyloxy carbomethoxy, carboethoxy or carbopropoxy.
 3. Adisazo dyestuff as claimed in claim 9 of the Formula
 4. A disazodyestuff as claimed in claim 3, wherein X1 represents hydrogen and R1and R3 each represent lower alkyl containing not more than 4 carbonatoms or acetyloxy substituted lower alkyl.
 5. A disazo dyestuff asclaimed in claim 1 of the formula
 6. A disazo dyestuff as claimed inclaim 1, wherein D2 represents the formula
 7. A disazo dyestuff asclaimed in claim 1, wherein the substituent on D1 and D2 ischloroacetylamino, Alpha , Beta -dibromopropionylamino, acrylamino,Alpha -bromoacrylamino or Beta -sulphatopropionylamino.